Polyol(allyl carbonate) composiitons and articles prepared there from

Abstract

Describes organic resin compositions of from about 30 to 90 weight percent of a polyol(allyl carbonate), e.g., diethylene glycol bis(allyl carbonate), and from about 10 to 70, e.g., 10 to 30, weight percent of a mixture of aliphatic urethanes, the terminal portions of which contain allyl or acrylyl functional groups. Polymerizable compositions prepared from such compositions produce castings which have low yellowness (b*) values and which do not pre-release from the molds in which they are formed. Polymerizates prepared from such compositions may be used to prepare photochromic articles, e.g., lenses, by incorporating a photochromic substance, e.g., by thermal transfer, into the polymerizate.

What is claimed is: 
     
       1. A polymerizable organic composition comprising a copolymerizable blend of: (a) polyol(allyl carbonate), and   (b) from about 10 to about 70 weight percent of a mixture of aliphatic urethanes, the terminal portions of which contain a functional group selected from the group consisting of allyl and acrylyl groups, said mixture of aliphatic urethanes being representable by at least two of the expressions, ##STR4## wherein D represents the terminal portion containing the allyl group, D' represents the terminal portion containing the acrylyl group, B represents an aliphatic bis carbamic moiety representable by the formula, --OC(O)--NH(E)NH--C(O)--O--, wherein E is the aliphatic residue of an aliphatic diisocyanate, and A in each aliphatic urethane present in the mixture of aliphatic urethanes represents the residue of a saturated aliphatic diol selected from the group consisting of C 2  -C 6  alkane diols, diethylene glycol, polyester diol, polyether diol or polycarbonate diol, the mole ratio of said allyl groups to acrylyl groups in the aliphatic urethanes present in the mixture being from about 15:1 to about 1:1.   
     
     
       2. The polymerizable composition of claim 1 wherein the polyol(allyl carbonate) is diethylene glycol bis(allyl carbonate) and the mixture of aliphatic urethanes is present in amounts of from about 10 to about 30 weight percent. 
     
     
       3. The polymerizable composition of claim 1 wherein A is the residue of a saturated polyester diol, having a molecular weight of from about 400 to about 1000, or C 2  -C 6  alkane diol. 
     
     
       4. The polymerizable composition of claim 3 wherein the polyester diol is poly(caprolactone) diol. 
     
     
       5. The polymerizable composition of claim 3 wherein the alkane diol is 1,4-butane diol. 
     
     
       6. The polymerizable composition of claim 1 wherein the aliphatic diisocyanate is isophorone diisocyanate. 
     
     
       7. The polymerizable composition of claim 2 wherein A is the residue of a saturated polyester diol having a molecular weight of from about 400 to about 1000, or a C 2  -C 6  alkane diol. 
     
     
       8. The polymerizable composition of claim 7 wherein the polyester diol is poly(caprolactone) diol, the alkane diol is 1,4-butane diol, and the aliphatic diisocyanate is isophorone diisocyanate. 
     
     
       9. The polymerizable composition of claim 8 wherein D is the allyl group and D' is the acrylyl group, CH 2  ═C(L)--C(O)--O--CH 2  --CH 2  --, wherein L is hydrogen or methyl. 
     
     
       10. The polymerizable composition of claim 1 wherein D is the allyl group and D' is the acrylyl group, CH 2  ═C(L)--C(O)--O--CH 2  --CH 2  --, wherein L is hydrogen or methyl. 
     
     
       11. The polymerizable composition of claim 3 wherein D is the allyl group, D' is the acrylyl group, CH 2  ═C(L)--C(O)--O--CH 2  --CH 2  --, wherein L is hydrogen or methyl, the polyester diol is poly(caprolactone) diol and the alkane diol is 1,4-butane diol. 
     
     
       12. The polymerizable composition of claim 2 wherein the mixture of aliphatic urethanes comprises a mixture of urethanes representable by the expressions,   ______________________________________                                    
          (1) D-B-A'-B-D,                                                 
          (2) D-B-A"-B-D,                                                 
          (3) D'-B-A'-B-D, and                                            
          (4) D'-B-A"-B-D                                                 
______________________________________                                    
     wherein A' is a..polyester diol and A" is a C 2  -C 6  alkane diol.   
     
     
       13. The polymerizable composition of claim 12 wherein the polyester diol is poly(caprolactone) diol having a molecular weight of from about 400 to about 1000, and the alkane diol is 1,4-butane diol. 
     
     
       14. The polymerizable composition of claim 13 wherein D is the allyl group and D' is the acrylyl group, CH 2  ═C(L)--C(O)--O--CH 2  --CH 2  --, wherein L is hydrogen or methyl. 
     
     
       15. The polymerizable composition of claim 14 wherein the aliphatic diisocyanate is isophorone diisocyanate. 
     
     
       16. The polymerizable composition of claim 2 wherein the mixture of aliphatic urethanes comprises a mixture of urethanes representable by the expressions,   ______________________________________                                    
          (1) D-B-A'-B-D,                                                 
          (2) D-B-A'-B-D', and                                            
          (3) D'-B-A'-B-D'                                                
______________________________________                                    
     wherein A' is a polyester diol.   
     
     
       17. The polymerizable composition of claim 16 wherein the polyester diol is poly(caprolactone) diol having a molecular weight of from about 400 to about 1000. 
     
     
       18. The polymerizable composition of claim 17 wherein D is the allyl group and D' is the acrylyl group, CH 2  =C(L)--C(O)--O--CH 2  --CH 2  --, wherein L is hydrogen or methyl. 
     
     
       19. The polymerizable composition of claim 18 wherein the aliphatic diisocyanate is isophorone diisocyanate. 
     
     
       20. The polymerizable composition of claim 2 wherein the composition contains from about 0.1 to about 0.5 weight percent, based on the weight of the copolymerizable blend, of dialkyl pyrocarbonate representable by the formula, R"--O--C(O)--O--C(O)--O--R", wherein R" is selected from the group consisting of C 1  -C 12  alkyl and C 6  -C 10  cycloalkyl. 
     
     
       21. The polymerizable composition of claim 20 wherein the dialkyl pyrocarbonate is diethyl pyrocarbonate. 
     
     
       22. The polymerizable composition of claim 12 wherein the composition contains from about 0.1 to about 0.5 weight percent, based on the weight of the copolymerizable blend, of dialkyl pyrocarbonate representable by the formula, R"--O--C(O)--O--C(O)--O--R", wherein R" is selected from the group consisting of C 1  -C 12  alkyl and C 6  -C 10  cycloalkyl. 
     
     
       23. The polymerizable composition of claim 22 wherein the dialkyl pyrocarbonate is diethyl pyrocarbonate. 
     
     
       24. The polymerizable composition of claim 16 wherein the composition contains from about 0.1 to about 0.5 weight percent, based on the weight of the copolymerizable blend, of dialkyl pyrocarbonate representable by the formula, R"--O--C(O)--O--C(O)--O--R", wherein R" is selected from the group consisting of C 1  -C 12  alkyl and C 6  -C 10  cycloalkyl. 
     
     
       25. The polymerizable composition of claim 24 wherein the dialkyl pyrocarbonate is diethyl pyrocarbonate. 
     
     
       26. A solid organic resin prepared by polymerizing the composition of claim 2. 
     
     
       27. The solid organic resin of claim 26 which contains a photochromic amount of an organic photochromic substance selected from the group consisting of spiro(indolino)naphthoxazines, spiro(indolino)pyridobenzoxazines, spiro(indolino)benzoxazines, spiro(indolino)benzopyrans, spiro(indolino)naphthopyrans, chromenes, spiro(benzindolino)pyridobenzoxazines, spiro(benzindolino)-naphthoxazines, spiro(benzindolino)naphthopyrans, metal dithizonates, fulgides, fulgimides, spiro(di)hydroindolizines, and mixtures of such photochromic substances. 
     
     
       28. The solid organic resin of claim 27, wherein the photochromic substance is selected from the group consisting of spiro(indolino)naphthoxazines, spiro(indolino)pyridobenzoxazines, spiro(indolino)benzoxazines, chromenes and mixtures of such photochromic substances. 
     
     
       29. A solid organic resin prepared by polymerizing the composition of claim 12. 
     
     
       30. A solid organic resin prepared by polymerizing the composition of claim 16.